Production System and Method of Production for Organic Compound or Microorganism

ABSTRACT

Provided is a novel production system that does not involve, or can minimize, the transport of liquid ammonia in the production of an organic compound or the production of a microorganism by microbial fermentation. A production system for an organic compound or a microorganism includes: an ammonia synthesis apparatus in which an ammonia-containing gas is synthesized by reaction of a source gas containing hydrogen and nitrogen in the presence of a supported ruthenium catalyst; and a culture apparatus that cultures a microorganism having organic compound productivity using ammonia originating from the ammonia-containing gas obtained by using the ammonia synthesis apparatus.

This application is a Continuation of, and claims priority under 35U.S.C. §120 to, International Application No. PCT/JP2016/054611, filedFeb. 17, 2016, and claims priority therethrough under 35 U.S.C. §119 toJapanese Patent Application No. 2015-028959, filed Feb. 17, 2015, theentireties of which are incorporated by reference herein.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to a production system and a method ofproduction for an organic compound or a microorganism.

Brief Description of the Related Art

Techniques for culturing microorganisms having the ability to produceorganic compounds are widely reported in the literature. See WO2006/038695, Japanese Patent Application Laid-open No. 2010-017082, and“Aminosan Hakko Gijutu no Keitouka Chousa”, National Museum of Scienceand Nature, Gijutu no Keitouka Chousa Houkoku Vol. 11, IndependentAdministrative Agency National Museum of Science and Nature, Mar. 19,2008, pp. 55-90, for example. The majority of amino acids in globaldistribution have been produced by fermentation methods for amino acids.Techniques are known that produce various kinds of organic compoundssuch as polysaccharides, proteins, antibiotics, alcohols, acrylamide,and diene compounds apart from amino acids by microbial fermentation,and research and development thereon are still currently being advanced.

In microbial fermentation, ammonia and nitrogen-containing compoundsoriginating from ammonia, such as ammonium salts, urea, nitric acid, andnitrates, for example, are generally used as a nitrogen source and a pHadjuster (See “Hakko Kogaku no Kiso Jikkensitsu kara Kojo made”, GakkaiShuppan Senta, September of 1988, pp. 78-81).

SUMMARY OF THE INVENTION

The use of microbial fermentation for production of organic compounds isincreasing globally, and the amount of ammonia used as the nitrogensource and as the pH adjuster also is increasing.

Ammonia is mainly produced by a large-scale production process, such asby the Haber-Bosch process. In the Haber-Bosch process, a source gascontaining hydrogen and nitrogen reacts under high-temperature,high-pressure conditions at 400° C. to 600° C. and 20 MPa to 100 MPausing a doubly promoted iron catalyst obtained by adding a few percentby weight of Al₂O₃ and K₂O to Fe₃O₄ to synthesize ammonia.

Global demand for ammonia for use as a raw material in production ofvarious kinds of chemical products and fertilizers, apart from microbialfermentation, is increasing; and therefore, production plants forsynthesizing ammonia are increasingly upsizing. The synthesis of ammoniaby such a large-scale production process assumes that the resultingammonia is liquefied and stored and is transported as liquid ammonia toammonia consumption sites. In addition to the costs of ammonia synthesisitself, also required are costs associated with the storage, transport,and maintenance of liquid ammonia, and these prices tend to be high.

To scale up the microbial fermentation process, procurement of ammoniato be used as the nitrogen source and the pH adjuster in the large-scaleprocess is necessary at a low price and in a sufficient amount.

It is an aspect of the present invention to provide a novel productionsystem and a method of production that do not involve, or can minimize,the transport of liquid ammonia in the production of organic compoundsby microbial fermentation.

In microorganism fermentation, microorganisms grow utilizing a carbonsource, a nitrogen source, or the like. In that sense, it is an aspectof the present invention to provide a novel production system and amethod of production that do not involve, (or can minimize, thetransport of liquid ammonia in the production of microorganisms.

It is an aspect of the present invention to provide a production systemuseful for reacting a source gas and a ruthenium catalyst to produce anorganic compound or a microorganism, the production system comprising:A) an ammonia synthesis apparatus configured to react a source gascomprising hydrogen and nitrogen in the presence of a ruthenium catalystand a support, wherein an ammonia-containing gas is synthesized; and B)a culture apparatus that is configured to culture a microorganism ableto produce an organic compound using ammonia originating from saidammonia-containing gas.

It is a further aspect of the present invention to provide the system asdescribed above, wherein said ammionia synthesis apparatus is configuredto react the source gas under conditions comprising a reactiontemperature of 530° C. or lower and a reaction pressure of 30 MPa orlower.

It is a further aspect of the present invention to provide the system asdescribed above, further comprising an ammonia concentration apparatusthat is configured to concentrate the ammonia from theammonia-containing gas.

It is a further aspect of the present invention to provide the system asdescribed above, further comprising a recycle apparatus that isconfigured to recover unreacted hydrogen and nitrogen following saidreaction in the ammonia synthesis apparatus, and is also configured toreturn said unreacted hydrogen and nitrogen to be reacted again in theammonia synthesis apparatus.

It is a further aspect of the present invention to provide the system asdescribed above, wherein the recycle apparatus comprises a dehydratorand/or a drier configured to remove water from said unreacted hydrogenand nitrogen.

It is a further aspect of the present invention to provide the system asdescribed above, wherein the production system is configured to produceammonia water using the ammonia originating from said ammonia-containinggas and is also configured to culture a microorganism able to produce anorganic compound using said ammonia water.

It is a further aspect of the present invention to provide the system asdescribed above, wherein the production system is configured to: produceammonia water using the ammonia originating from said ammonia-containinggas, recover ammonia gas from said ammonia water, and culture amicroorganism able to produce an organic compound using said ammoniagas.

It is a further aspect of the present invention to provide the system asdescribed above, wherein ammonia is used as a nitrogen source or a pHadjuster in the culture apparatus.

It is a further aspect of the present invention to provide the system asdescribed above, wherein the microorganism is able to produce an organiccompound selected from the group consisting of amino acids, organicacids, polysaccharides, proteins, antibiotics, and alcohols.

It is a further aspect of the present invention to provide the system asdescribed above, wherein the microorganism is a bacterium or a fungus.

It is a further aspect of the present invention to provide a method ofproduction for a produce selected from the group consisting of anorganic compound and a microorganism, the method comprising the stepsof: (A) reacting a source gas comprising hydrogen and nitrogen in thepresence of a ruthenium catalyst and a support, wherein an ammonia gasis synthesized; and (B) culturing a microorganism able to produce anorganic compound using ammonia originating from said ammonia-containinggas.

It is a further aspect of the present invention to provide the method asdescribed above, wherein step (A) and step (B) are successivelyperformed.

It is a further aspect of the present invention to provide the method asdescribed above, wherein the source gas reacts under conditionscomprising a reaction temperature of 530° C. or lower and a reactionpressure of 30 MPa or lower in step (A).

It is a further aspect of the present invention to provide the method asdescribed above, further comprising concentrating ammonia within theammonia-containing gas obtained in step (A).

It is a further aspect of the present invention to provide the method asdescribed above, further comprising recovering unreacted hydrogen andnitrogen after step (A) and recycling said unreacted hydrogen andnitrogen to step (A).

It is a further aspect of the present invention to provide the method asdescribed above, wherein the recycling comprises performing dehydrationtreatment and/or drying treatment to remove water from said unreactedhydrogen and nitrogen.

It is a further aspect of the present invention to provide the method asdescribed above, wherein ammonia water is produced using ammoniaoriginating from the ammonia-containing gas obtained in step (A) and amicroorganism able to produce an organic compound is cultured using theobtained ammonia water in step (B).

It is a further aspect of the present invention to provide the method asdescribed above, wherein ammonia water is produced using ammoniaoriginating from the ammonia-containing gas obtained in step (A),ammonia gas is recovered from the obtained ammonia water, and amicroorganism able to produce an organic compound is cultured using saidammonia gas in step (B).

It is a further aspect of the present invention to provide the method asdescribed above, wherein ammonia is used as a nitrogen source or a pHadjuster in step (B).

It is a further aspect of the present invention to provide the method asdescribed above, wherein the microorganism is able to produce an organiccompound selected from the group consisting of amino acids, organicacids, polysaccharides, proteins, antibiotics, and alcohols.

It is a further aspect of the present invention to provide the method asdescribed above, wherein the microorganism is a bacterium or a fungus.

The present invention can provide a novel production system and a methodof production for an organic compound or a microorganism that do notinvolve (or can minimize) the transport of liquid ammonia.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic diagram (1) of a production system in oneembodiment of the present invention.

FIG. 2 is a schematic diagram (2) of a production system in oneembodiment of the present invention.

FIG. 3 is a schematic diagram (3) of a production system in oneembodiment of the present invention.

FIG. 4 is a schematic diagram (4) of a production system in oneembodiment of the present invention.

DESCRIPTION OF THE EXEMPLARY EMBODIMENTS

The following describes the present invention in detail in conformitywith exemplary embodiments thereof.

The present invention provides a novel production system for an organiccompound or a microorganism.

As described above, ammonia synthesis by a large-scale production systemassumes that the synthesized ammonia is liquefied, and then stored andtransported in liquid form to ammonia consumption sites, and peripheralcosts associated with the storage, transport and maintenance of liquidammonia are increasing.

When ammonia is used as a nitrogen source or a pH adjuster in microbialfermentation, it is typically produced at the site where the microbialfermentation is performed, that is, produced on site. In this way,organic compounds or microorganisms can be produced by microbialfermentation without the storage and transport of liquid ammonia.

In one embodiment, the production system for an organic compound or amicroorganism can include:

an ammonia synthesis apparatus that is configured to produce anammonia-containing gas by reaction of a source gas containing hydrogenand nitrogen in the presence of a supported ruthenium catalyst; and

a culture apparatus that is configured to culture a microorganism ableto produce an organic compound using ammonia originating from theammonia-containing gas obtained by using the ammonia synthesisapparatus.

<Ammonia Synthesis Apparatus>

In the ammonia synthesis apparatus of the production system, the sourcegas containing hydrogen and nitrogen is reacted in the presence of theruthenium catalyst and a support to synthesize the ammonia-containinggas.

As described above, ammonia is currently produced mainly by theHaber-Bosch process. In the Haber-Bosch process, a source gas containinghydrogen and nitrogen reacts under high-temperature, high-pressureconditions at 400° C. to 600° C. and 20 MPa to 100 MPa using a doublypromoted iron catalyst to synthesize ammonia.

The production system as described herein uses the ruthenium catalyst asan ammonia synthesis catalyst. The ruthenium catalyst can exhibit higherammonia synthesis activity even under low pressure conditions than thedoubly promoted iron catalyst used in the Haber-Bosch process.

The support for the ruthenium catalyst is not limited to a particularsupport so long as it can support ruthenium and does not hinder thecatalytic activity of ruthenium in the ammonia synthesis; any knownsupport may be used. Examples of the support can include oxides such assilicon oxide (silica), zinc oxide, aluminum oxide (alumina), magnesiumoxide (magnesia), indium oxide, calcium oxide, zirconium oxide(zirconia), titanium oxide (titania), boron oxide, hafnium oxide, bariumoxide, cerium oxide (ceria), and zeolite; nitrides such as siliconnitride, aluminum nitride, boron nitride, and magnesium nitride; andactive carbon. One support may be used alone, or two or more supportsmay be used in combination.

The ruthenium catalyst may contain one or more of the followingelements: alkaline metals, alkaline earth metals, and rare earth metalsas a promoter component.

In view of ammonia synthesis activity, the amount of ruthenium in theruthenium catalyst can be 0.01 wt % or higher, 0.02 wt % or higher, 0.03wt % or higher, 0.05 wt % or higher, 0.1 wt % or higher, 0.3 wt % orhigher, 0.5 wt % or higher, or 1 wt % or higher when the support is 100wt %. To lessen the sintering of ruthenium particles during the ammoniasynthesis reaction so to retain the expected ammonia synthesis activity,the upper limit of the amount of ruthenium can be 30 wt % or lower, 20wt % or lower, 15 wt % or lower, or 10 wt % or lower.

When the promoter component is used, the amount of the promotercomponent in the ruthenium catalyst is not limited to a particularamount, but can be 0.01 wt % to 1,000 wt % or 1 wt % to 800 wt % whenruthenium is 100 wt %, in view of ammonia synthesis activity.

The specific surface area of the ruthenium catalyst, which is notlimited to a particular value, can be 0.1 m²/g to 1,000 m²/g or 0.5 m²/gto 800 m²/g. The specific surface area of the ruthenium catalyst can bemeasured by a BET adsorption method, for example.

A method of preparation for the ruthenium catalyst on the support is notlimited to a particular method; an appropriate method may be selectedfrom known methods in accordance with the type of chosen support and thelike. Examples of the method can include an impregnation process, asol-gel process, CVD, and sputtering.

In the production system, the ammonia synthesis apparatus is not limitedto a particular configuration so long as it is configured to react thesource gas containing hydrogen and nitrogen in the presence of theruthenium catalyst and support to synthesize ammonia gas, and theapparatus can include an inlet for the source gas containing hydrogenand nitrogen, a reaction unit in which the source gas reacts in thepresence of the catalyst to synthesize the ammonia-containing gas, andan outlet for the produced ammonia-containing gas, for example.

In the reaction unit of the ammonia synthesis apparatus, hydrogen andnitrogen in the source gas directly react in accordance with a formula:3H₂+N₂<

2H₃ under the effect of the catalyst to synthesize ammonia.

In view of making ammonia synthesis at the ammonia consumption siteseasy, the reaction temperature can be 600° C. or lower, 550° C. orlower, 530° C. or lower, 500° C. or lower, 450° C. or lower, or 400° C.or lower. In view of ammonia synthesis activity, the lower limit of thereaction temperature can be 100° C. or higher, 150° C. or higher, 200°C. or higher, 250° C. or higher, or 300° C. or higher.

In view of making ammonia synthesis at the ammonia consumption siteseasy, the reaction pressure can be 30 MPa or lower, 25 MPa or lower, or20 MPa or lower. The supported ruthenium catalyst can achieve excellentammonia synthesis activity even when the reaction pressure is furtherlowered. The reaction pressure may be 15 MPa or lower, 10 MPa or lower,5 MPa or lower, 4 MPa or lower, 3 MPa or lower, 2 MPa or lower, or 1 MPaor lower, for example. In view of the ammonia concentration at theoutlet of the ammonia synthesis apparatus governed by chemicalequilibrium in one preferred embodiment, the lower limit of the reactionpressure can be 10 kPa or higher, 50 kPa or higher, or 100 kPa orhigher. The reaction pressure is a gauge pressure (the same applies tothe following).

In the reaction unit of the ammonia synthesis apparatus, the reactionmode may be any of a batch reaction mode, a closed circulatory systemreaction mode, and a flow system reaction mode; in view of practicality,the flow system reaction mode is preferred. Known reactor structures canbe employed such as an internal heat exchange type for the purpose ofretaining an ammonia synthesis reaction rate at a high level bycontrolling an increase in the temperature of a catalyst layer byreaction and increasing equilibrium ammonia concentration and a quenchertype that supplies the source gas in a divided manner in a fluid flowdirection.

In the reaction unit of the ammonia synthesis apparatus, one rutheniumcatalyst may be used alone, or two or more ruthenium catalysts may beused in combination. Alternatively, two or more catalysts including thesupported ruthenium catalyst and other ammonia synthesis catalysts maybe used in combination. When two or more catalysts are used, inaccordance with a reaction mode, the two or more catalysts may be usedafter mixing them with each other, the catalysts may be used by stackingso as to form separate layers by type, or the catalysts may be filledinto separate reaction tubes so as to be filled into different reactiontubes by type and then used by combining the reaction tubes.

When the supported ruthenium catalyst is used, in obtaining expectedammonia synthesis activity, it is important to reduce the water contentwithin the source gas. In view of the stability of the catalyst inparticular, the water content within the source gas can be 100 ppm byvolume or lower or 50 ppm by volume or lower. The lower limit of thewater content can be lower and may be 0 ppm by volume. When theproduction system includes a recycle apparatus for unreacted hydrogenand nitrogen described below, it is important that the water contentwithin the source gas is within the range including a water contentwithin gas recovered by the recycle apparatus.

The molar ratio (hydrogen/nitrogen) between hydrogen and nitrogen withinthe source gas can be 1/2 to 5/1, 1/2 to 3/1, 1/2 to 2/1, or 4/5 to 6/5.

Hydrogen within the source gas used for ammonia synthesis can beprepared by commonly known methods such as 1) a method that transforms ahydrocarbon (coal, petroleum, natural gas, or biomass, for example) intogas containing CO and H₂ by a steam reforming reaction, a partialoxidation reaction, or a combination of these reactions and thenperforms a CO shift reaction and decarbonation processing, 2) a methodthat electrolyzes water, and 3) a method that decomposes water using aphotocatalyst. Alternatively, hydrogen may be supplied from a hydrogencylinder, including a hydrogen cylinder curdle, the same applies to thefollowing, or a hydrogen tank, including a mobile tank such as ahydrogen self-loader, the same applies to the following. Nitrogen withinthe source gas used for ammonia synthesis may be prepared by separatingnitrogen from air using a nitrogen separation membrane or a cryogenicseparation method. Alternatively, when hydrogen is prepared utilizingthe partial oxidation reaction of the hydrocarbon, nitrogen within airused as an oxygen source may be utilized. Alternatively, nitrogen may besupplied from a nitrogen cylinder, including a nitrogen cylinder curdle,the same applies to the following, or a nitrogen tank, including amobile tank such as a nitrogen self-loader, the same applies to thefollowing.

The source gas containing hydrogen and nitrogen can be prepared using aprocess that can be performed advantageously at the ammonia consumptionsites.

In the production system, ammonia concentration within theammonia-containing gas synthesized by the ammonia synthesis apparatuscan be 0.5% by volume or higher, 2% by volume or higher, 4% by volume orhigher, 6% by volume or higher, 8% by volume or higher, or 10% by volumeor higher. The ammonia-containing gas synthesized by the ammoniasynthesis apparatus mainly contains unreacted hydrogen and unreactednitrogen apart from ammonia.

In the production system of, the ammonia synthesis capacity(ammonia-ton/day) of the ammonia synthesis apparatus, which varies bythe amount of ammonia usage in the culture apparatus, can be 300 ton/dayor less, 200 ton/day or less, 100 ton/day or less, 80 ton/day or less,60 ton/day or less, or 50 ton/day or less. The lower limit of theammonia synthesis capacity, which is not limited to a particular amount,can be normally 0.1 ton/day or more, 1 ton/day or more, 2 ton/day ormore, or the like.

In the production system, microorganisms having organic compoundproductivity are cultured using ammonia originating from theammonia-containing gas obtained by using the ammonia synthesisapparatus. In culture, ammonia is used as the nitrogen source or the pHadjuster.

The ammonia-containing gas obtained by using the ammonia synthesisapparatus may be 1) supplied to the culture apparatus directly afterbeing cooled or 2) supplied to the culture apparatus as concentratedammonia gas or liquid ammonia, or ammonia water as needed, after beingconcentrated, or 3) ammonia gas may be recovered from the obtainedammonia water, and the recovered ammonia gas may be supplied to theculture apparatus. In the 2) and 3) embodiments, using ammonia“originating from” the ammonia-containing gas obtained by using theammonia synthesis apparatus is envisioned. Ammonia may also be suppliedto the culture apparatus after being transformed intonitrogen-containing compounds originating from ammonia includingammonium salts such as ammonium sulfate, nitric acid, and nitrates. Insuch an embodiment, ammonia is used as a raw material of the nitrogensource or the pH adjuster. Such an embodiment is also included in theexpression “ammonia is used as the nitrogen source or the pH adjuster”.

Consequently, in one embodiment, the production system further includesa cooler that cools the ammonia-containing gas obtained by using theammonia synthesis apparatus. The cooler is not limited to a particularcooler so long as it can cool the ammonia-containing gas to a certaintemperature; any of known coolers, a coil type heat exchanger or ashell-and-tube type heat exchanger, for example, may be used. The cooledammonia-containing gas may be supplied to the culture apparatus as it isor supplied to the culture apparatus after being stored in a storagetank.

In another embodiment, the production system further includes an ammoniaconcentration apparatus that concentrates the ammonia within theammonia-containing gas obtained by using the ammonia synthesisapparatus. The ammonia concentration apparatus is not limited to aparticular apparatus so long as it can concentrate the ammonia withinthe ammonia-containing gas; any known concentration apparatuses may beused. Examples of the ammonia concentration apparatus can include apressurized cooling apparatus, a gas separation membrane apparatus, anda pressure swing adsorption (PSA) apparatus.

When the pressurized cooling apparatus is used as the ammoniaconcentration apparatus, the conditions of pressurized cooling aresuitably set so as to liquefy the ammonia within the ammonia-containinggas. Pressure during the pressurized cooling, which varies by reactionpressure in the reaction unit of the ammonia synthesis apparatus andtemperature during the pressurized cooling, can be 10 kPa or higher, 50kPa or higher, 100 kPa or higher, 0.2 MPa or higher, 0.3 MPa or higher,0.4 MPa or higher, or 0.5 MPa or higher. The temperature during thepressurized cooling, which varies by the pressure during the pressurizedcooling, can be 50° C. or lower, 40° C. or lower, 30° C. or lower, 20°C. or lower, 10° C. or lower, 5° C. or lower, 0° C. or lower, −5° C. orlower, or −10° C. or lower. The lower limit of the temperature, which isnot limited to a particular temperature, can be normally −35° C. orhigher, −30° C. or higher, or the like. The pressurized coolingapparatus is not limited to a particular apparatus so long as it canperform pressurized cooling of the ammonia-containing gas obtained byusing the ammonia synthesis apparatus on the conditions; any of knownpressurized cooling apparatuses may be used. Liquid ammonia obtained bypressurized cooling of the ammonia-containing gas may be supplied to theculture apparatus as it is or supplied to the culture apparatus afterbeing stored in a storage tank.

When the gas separation membrane apparatus is used as the ammoniaconcentration apparatus, a hydrogen gas separation membrane, a nitrogengas separation membrane, or a combination of these membranes is suitablyused. The ammonia-containing gas obtained by using the ammonia synthesisapparatus mainly contains ammonia, unreacted hydrogen, and unreactednitrogen, and at least either the unreacted hydrogen or the unreactednitrogen is separated by the gas separation membrane, whereby theammonia can be concentrated. The hydrogen gas separation membrane andthe nitrogen gas separation membrane are not limited to particularmembranes so long as they can separate the unreacted hydrogen ornitrogen within the ammonia-containing gas obtained by using the ammoniasynthesis apparatus; any known hydrogen gas separation membranes andnitrogen gas separation membranes may be used. Alternatively, an ammoniagas separation membrane that can selectively separate the ammonia withinthe ammonia-containing gas may be used. In concentrating ammonia usingthe gas separation membrane apparatus, conditions including temperatureand pressure may be determined in accordance with the chosen gasseparation membrane. Pressure, on a crude gas side, during gasseparation can be 10 kPa or higher, 50 kPa or higher, 100 kPa or higher,0.2 MPa or higher, 0.3 MPa or higher, 0.4 MPa or higher, or 0.5 MPa orhigher, for example. The upper limit of the gas pressure, on the crudegas side, which is not limited to a particular pressure, is normally thereaction pressure in the reaction unit of the ammonia synthesisapparatus or lower. The concentrated ammonia gas obtained by the gasseparation membrane apparatus may be supplied to the culture apparatusas it is or supplied to the culture apparatus after being stored in astorage tank.

The pressure swing adsorption (PSA) apparatus may be used as the ammoniaconcentration apparatus. The PSA apparatus uses an adsorbent exhibitingselective adsorbability for the ammonia within the ammonia-containinggas and controls the adsorption and desorption of the ammonia bypressure change to separate the ammonia from the other gases toconcentrate the ammonia. The PSA apparatus is not limited to aparticular apparatus so long as it can concentrate the ammonia withinthe ammonia-containing gas; any known PSA apparatuses may be used. Theammonia within the ammonia-containing gas may be concentrated using aPSA apparatus described in Japanese Patent No. 2634015, for example.

In the PSA apparatus, pressure (P_(ad)) when the ammonia is adsorbed tothe adsorbent and pressure (P_(de)) when the ammonia is desorbed fromthe adsorbent can satisfy P_(ad)>P_(de). In view of efficientlyconcentrating the ammonia within the ammonia-containing gas, P_(ad) andP_(de) can satisfy P_(ad)-P_(de≧)10 kPa, P_(ad)-P_(de)≧50 kPa,P_(ad)-P_(de)≧100 kPa, P_(ad)-P_(de)≧0.2 MPa, P_(ad)-P_(de)≧0.3 MPa,P_(ad)-P_(de)≧0.4 MPa, or P_(ad)-P_(de) 0.5 MPa. The upper limit of thedifference (P_(ad)-P_(de)) between P_(ad) and P_(de) is normally thereaction pressure in the reaction unit of the ammonia synthesisapparatus or lower. P_(ad), which is not limited to a particularpressure so long as it satisfies P_(ad) >P_(de), may be determined inaccordance with the adsorbability of the adsorbent used and is normallythe reaction pressure in the reaction unit of the ammonia synthesisapparatus or less. P_(de), which is not limited to a particular pressureso long as it satisfies P_(ad)>P_(de), may be determined in accordancewith the adsorbability of the adsorbent used and is normally 1 MPa orlower, 0.5 MPa or lower, 0.2 MPa or lower, 100 kPa or lower, 50 kPa orlower, 10 kPa or lower, or 0 kPa or lower. Temperature during the gasseparation may be determined in accordance with the specificspecification of the PSA apparatus.

When the PSA apparatus is used as the ammonia concentration apparatus,the PSA apparatus suitably includes two or more adsorption towers. ThePSA apparatus including two adsorption towers, a first adsorption towerand a second adsorption tower, for example, is operated so as to performan ammonia desorption process in the second adsorption tower when anammonia adsorption process is performed in the first adsorption towerand perform the ammonia adsorption process in the second adsorptiontower when the ammonia desorption process is performed in the firstadsorption tower, whereby the ammonia within the ammonia-containing gascan be continuously concentrated. The concentrated ammonia gas obtainedby the PSA apparatus may be supplied to the culture apparatus as it isor supplied to the culture apparatus after being stored in a storagetank.

When the PSA apparatus is used as the ammonia concentration apparatus,ammonia concentration within the concentrated ammonia gas obtained bythe ammonia concentration apparatus can be 10% by volume or higher, 30%by volume or higher, 50% by volume or higher. The upper limit of theammonia concentration can be higher and may be 100% by volume.Consequently, the “concentrating” of ammonia is a concept that includesthe isolation of the ammonia from the ammonia-containing gas.

The ammonia-containing gas obtained by using the ammonia synthesisapparatus may be further purified using an ammonia purificationapparatus after the ammonia is concentrated by the ammonia concentrationapparatus.

As described above, the ammonia-containing gas obtained by using theammonia synthesis apparatus contains the unreacted hydrogen and theunreacted nitrogen. These unreacted hydrogen and nitrogen are recycledas sources of ammonia synthesis, whereby system efficiency can beimproved. Consequently, in one embodiment, the production system furtherincludes a recycle apparatus that recovers the unreacted hydrogen andnitrogen on the downstream side of the ammonia synthesis apparatus andrecycles a recovered gas to the upstream side of the ammonia synthesisapparatus.

In the embodiment in which the ammonia-containing gas obtained by usingthe ammonia synthesis apparatus is supplied to the culture apparatus asit is after being cooled, the recycle apparatus may be provided in theculture apparatus. The details of the recycle apparatus will bedescribed below with reference to the drawings.

In the embodiment in which the ammonia-containing gas obtained by usingthe ammonia synthesis apparatus is concentrated and supplied as theconcentrated ammonia gas or liquid ammonia (or ammonia water as needed)to the culture apparatus, the unreacted hydrogen and nitrogen can beselectively recovered in the ammonia concentration apparatus, and therecycle apparatus may be provided in the ammonia concentrationapparatus.

The recycle apparatus is not limited to a particular apparatus so longas it can recover the unreacted hydrogen and nitrogen and recycle therecovered gas containing hydrogen and nitrogen to the upstream side ofthe ammonia synthesis apparatus; any known recycle apparatuses may beused. The recycle apparatus may include a pipe for the recovered gas anda pump for transporting the recovered gas, for example.

When the recovered gas contains water, if the gas is recycled as it is,the catalytic ability of the supported ruthenium catalyst used in theammonia synthesis apparatus may be affected. Consequently, in oneembodiment, the recycle apparatus can include a dehydrator that removesthe water within the recovered gas. The dehydrator is not limited to aparticular dehydrator so long as it can reduce the water content withinthe recovered gas to a value that does not affect the catalytic abilityof the supported ruthenium catalyst; any of known dehydrators may beused. Examples of the dehydrator can include an apparatus that cools therecovered gas to condense and remove the water. In view of furtherreducing the water content within the recovered gas, the recycleapparatus may use a drier and may include the drier in addition to thedehydrator or in place of the dehydrator. The drier is not limited to aparticular drier so long as it has a function of further reducing thewater content within the recovered gas; any known driers may be used.Examples of the drier can include an apparatus that brings the recoveredgas into contact with a moisture absorbent to perform dehydration;examples of the moisture absorbent in this apparatus can include, butare not limited to, chemical moisture absorbents such as calciumchloride, diphosphorus pentaoxide, and copper sulfate anhydride; andphysical moisture absorbents such as silica gel, alumina gel, andzeolite.

<Culture Apparatus>

In the production system, the culture apparatus cultures microorganismshaving organic compound productivity using ammonia originating from theammonia-containing gas obtained by using the ammonia synthesisapparatus.

Techniques for culturing microorganisms having organic compoundproductivity to produce organic compounds are widely known. The presentinvention can be applied widely to such microorganism fermentationtechniques. Examples of the organic compounds produced in microorganismfermentation can include amino acids, organic acids, polysaccharides,proteins, antibiotics, and alcohols. Examples of the amino acids caninclude glycine, alanine, valine, leucine, isoleucine, serine,threonine, cysteine, cystine, methionine, phenylalanine, tyrosine,tryptophan, proline, hydroxyproline, asparagine, glutamine, asparticacid, glutamic acid, lysine, histidine, and arginine. Examples of theorganic acids can include acetic acid, lactic acid, pyruvic acid,succinic acid, malic acid, itaconic acid, citric acid, acrylic acid,propionic acid, and fumaric acid. Examples of the polysaccharides caninclude xanthan, dextran, alginate, hyaluronic acid, curdlan, gellan,scleroglucan, and pullulan. Examples of the proteins can includehormones, lymphokines, interferons, and enzymes, such as amylase,glucoamylase, invertase, lactase, protease, and lipase. Examples of theantibiotics can include antimicrobial agents, such as β-lactams,macrolides, ansamycin, tetracycline, chloramphenicol, peptidergicantibiotics, and aminoglycosides, antifungal agents, such as polyoxin B,griseofulvin, and polyenemacrolides, anticancer agents, daunomycin,adriamycin, dactinomycin, mithramycin, and bleomycin, protease/peptidaseinhibitors, such as leupeptin, antipain, and pepstatin, and cholesterolbiosynthesis inhibitors, such as compactin, lovastatin, and pravastatin.Examples of the alcohols can include ethanol, isopropanol, glycerin,propylene glycol, trimethylene glycol, 1-butanol, and sorbitol. Otherexamples of the organic compounds produced in microorganism fermentationcan include acrylamide, diene compounds (such as isoprene), andpentanediamine.

The microorganisms having organic compound productivity can includeboth 1) microorganisms intrinsically having organic compoundproductivity and 2) microorganisms that have acquired organic compoundproductivity through the introduction of organic compound productiongenes by gene recombination although they do not have or do notsubstantially have organic compound productivity intrinsically. As tothe microorganisms having organic compound productivity, various kindsof microorganisms are known in accordance with the type of organiccompounds; these known microorganisms may be widely used. So long asammonia can be used as the nitrogen source or the pH adjuster inculture, the present invention can be widely applied also tomicroorganisms to be developed in the future.

The microorganisms, which are not limited to particular microorganismsso long as they have organic compound productivity, are preferablybacteria or fungi. Examples of the bacteria can include the Escherichiabacteria, the Pantoea bacteria, the Corynebacterium bacteria, theEnterobacter bacteria, the Clostridium bacteria, the Bacillus bacteria,the Lactobacillus bacteria, the Streptomyces bacteria, the Streptococcusbacteria, and the Pseudomonas bacteria. Examples of the fungi caninclude the Saccharomyces fungi, the Schizosaccharomyces fungi, theYarrowia fungi, the Trichoderma fungi, the Aspergillus fungi, theFusarium fungi, and the Mucor fungi.

Examples of the Escherichia bacteria can include Escherichia coli.Examples of the Pantoea bacteria can include Pantoea ananatis. Examplesof the Corynebacterium bacteria can include Corynebacterium glutamicumand Corynebacterium ammoniagenes. Examples of the Enterobacter bacteriacan include Enterobacter aerogenes. Examples of the Clostridium bacteriacan include Clostridium acetobutylicum. Examples of the Bacillusbacteria can include Bacillus subtilis and Bacillus amyloliquefaciens.Examples of the Lactobacillus bacteria can include Lactobacillusyamanashiensis, Lactobacillus animalis, Lactobacillus hilgardii, andLactobacillus brevis. Examples of the Streptomyces bacteria can includeStreptomyces clavuligerus, Streptomyces venezuelae, and Streptomycespeucetius. Examples of Streptococcus bacteria can include Streptococcusequi and Streptococcus mutans. Examples of the Pseudomonas bacteria caninclude Pseudomonas fluorescens, Pseudomonas aeruginosa, Pseudomonaselodea, and Pseudomonas putida. Examples of the Saccharomyces fungi caninclude Saccharomyces cerevisiae. Examples of the Schizosaccharomycesfungi can include Schizosaccharomyces pombe. Examples of the Yarrowiafungi can include Yarrowia lipolytica. Examples of the Trichoderma fungican include Trichoderma reesei. Examples of the Aspergillus fungi caninclude Aspergullus terreus and Aspergillus oryzae. Examples of theFusarium fungi can include Fusarium hetereosporum. Examples of the Mucorfungi can include Mucor javanicus.

When the production system produces amino acids, examples of themicroorganisms that can be suitably used can include the following: whenthe target substance is L-lysine, for example, examples thereof caninclude Escherichia coli A J11442 (NRRL B-12185, FERM BP-1543) (refer toU.S. Pat. No. 4,346,170), Brevibacterium lactofermentum AJ3990(ATCC31269) (refer to U.S. Pat. No. 4,066,501), and Lys-producingbacteria WC196LC/pCABD2 (WO 2010/061890). WC196ΔcadAΔldc is a strainconstructed by destroying the cadA and ldcC genes that code lysinedecarboxylase from the WC196 strain. WC196ΔcadAΔldc/pCABD2 is a strainconstructed by introducing a plasmid pCABD2 (U.S. Pat. No. 6,040,160)containing a lysine biosynthetic gene to WC196ΔcadAΔldc. WC196ΔcadAΔldcwas named AJ110692 and was deposited at International Patent OrganismDepositary, National Institute of Advanced Industrial Science andTechnology (currently Patent Microorganisms Depositary, NationalInstitute of Technology and Evaluation, No. 120, 2-5-8 Kazusakamatari,Kisarazu-shi, Chiba 292-0818, Japan) with an accession number of FERMBP-11027 on Oct. 7, 2008. Examples thereof for L-threonine can includeEscherichia coli VKPM B-3996 (RIA 1867, VKPM B-3996) (refer to U.S. Pat.No. 5,175,107) and Corynebacterium acetoacidophilum AJ12318 (FERMBP-1172) (refer to U.S. Pat. No. 5,188,949); examples thereof forL-phenylalanine can include Escherichia coli AJ12604 (FERM BP-3579)(refer to European Patent Application Laid-open No. 488,424), andBrevibacterium lactofermentum AJ12637 (FERM BP-4160) (refer to FrenchPatent Application Laid-open No. 2,686,898); examples thereof forL-glutamic acid can include Escherichia coli AJ12624 (FERM BP-3853)(refer to French Patent Application Laid-open No. 2,680,178) andBrevibacterium lactofermentum AJ12475 (FERM BP-2922) (refer to U.S. Pat.No. 5,272,067), and 2256ΔldhAΔsucAyggB* prepared with Corynebacteriumglutamicum ATCC13869 as a mother strain (WO 2014/185430); examplesthereof for L-leucine can include Escherichia coli AJ11478 (FERM P-5274)(refer to Japanese Examined Patent Application Publication No.S62-34397) and Brevibacterium lactofermentum AJ3718 (FERM P-2516) (referto U.S. Pat. No. 3,970,519); examples thereof for L-isoleucine caninclude Escherichia coli KX141 (VKPM B-4781) (refer to European PatentApplication Laid-open No. 519,113) and Brevibacterium flavum AJ12149(FERM BP-759) (refer to U.S. Pat. No. 4,656,135); and examples thereoffor L-valine can include Escherichia coli VL1970 (VKPM B-4411) (refer toEuropean Patent Application Laid-open No. 519,113) and Brevibacteriumlactofermentum AJ12341 (FERM BP-1763) (refer to U.S. Pat. No.5,188,948).

When the production system produces organic acids, examples of themicroorganisms that can be suitably used can include the following: whenthe target substance is L-lactic acid, for example, examples thereof caninclude Lactobacillus yamanashiensis, Lactobacillus animalis, andSaccharomyces cerevisiae; examples thereof for pyruvic acid can includeEscherichia coli and Pseudomonas fluorescens; examples thereof forsuccinic acid can include Escherichia coli and Pantoea ananatis;examples thereof for itaconic acid can include Aspergillus terreus; andexamples thereof for citric acid can include Escherichia coli (refer toWO 2007/097260 and Japanese Patent Application Laid-open No.2010-187542, for example).

When the production system produces polysaccharides, examples of themicroorganisms that can be suitably used can include the following: whenthe target substance is dextran, for example, examples thereof caninclude Lactobacillus hilgardii and Streptococcus mutans; examplesthereof for alginate can include Pseudomonas aeruginosa; examplesthereof for hyaluronic acid can include Streptococcus equi andStreptococcus mutans; and examples thereof for gellan can includePseudomonas elodea (refer to Japanese Patent Application Laid-open No.2011-116825 and Japanese Patent Application Laid-open No. 2007-9092, forexample).

When the production system produces proteins, examples of themicroorganisms that can be suitably used can include the following: whenthe target substance is any of various kinds of hormones or interferons,for example, examples thereof can include Saccharomyces cerevisiae;examples thereof for amylase, glucoamylase, protease, or lipase caninclude Bacillus subtilis and Aspergillus oryzae; and examples thereoffor invertase or lactase can include Saccharomyces cerevisiae andAspergillus oryzae (refer to WO 2006/67511 and Japanese PatentApplication Laid-open No. 2003-153696, for example).

When the production system produces antibiotics, examples of themicroorganisms that can be suitably used can include the following: whenthe target substance is a 13-lactam such as penicillin, for example,examples thereof can include Pseudomonas putida and Streptomycesclavuligerus; examples thereof for macrolides such as erythromycin andazithromycin can include Streptomyces venezuelae; examples thereof fordaunomycin can include Streptomyces peucetius; examples thereof forpravastatin can include Streptomyces clavuligerus (refer to WO 96/10084,Japanese Patent Application Laid-open No. 2002-53589, WO 2005/54265, andWO 2007/147827, for example).

When the production system produces alcohols, examples of themicroorganisms that can be used can include the following: when thetarget substance is ethanol, for example, examples thereof can includeSaccharomyces cerevisiae, Schizosaccharomyces pombe, and Lactobacillusbrevis; and examples thereof for trimethylene glycol can includeEscherichia coli (refer to WO 2007/97260, for example).

A medium for culturing microorganisms can contain a carbon source and anitrogen source for being converted into organic compounds. Examples ofthe carbon source can include carbohydrates such as monosaccharides,disaccharides, oligosaccharides, and polysaccharides; invert sugarsobtained by hydrolyzing sucrose; glycerol; C₁ compounds such asmethanol, formaldehyde, formates, carbon monoxide, and carbon dioxide;oils such as corn oil, palm oil, and soybean oil; acetates; animal fats;animal oils; fatty acids such as saturated fatty acids and unsaturatedfatty acids; lipids; phospholipids; glycerolipids; glycerin fatty acidesters such as monoglycerides, diglycerides, and triglycerides;polypeptides such as microbial proteins and vegetable proteins;renewable carbon sources such as a hydrolyzed biomass carbon source;yeast extracts; and combinations thereof. Examples of the nitrogensource can include inorganic nitrogen sources such as ammonia, ammoniumsalts, nitric acid, and nitrates; organic nitrogen sources such as urea,amino acids, and proteins; and combinations thereof. The medium cancontain inorganic ions and other organic minor components as needed inaddition to the carbon source and the nitrogen source. The inorganicions and the other organic minor components may be any known components.The medium may be a natural medium or a synthetic medium.

Culture conditions are not limited to particular conditions so long asthe conditions can produce a target organic compound; any standardmicroorganism culture conditions may be used. The culture temperaturecan be 20° C. to 37° C. In accordance with the characteristics of themicroorganism, culture can be performed under an aerobic, anoxic, oranaerobic condition.

As to the method of culture, known methods such as a batch culturemethod, a fed-batch culture method, and a continuous culture method maybe used.

A liquid depth, that is, the medium depth, in the culture apparatus maybe determined as appropriate in accordance with the characteristics ofthe microorganism. When the medium is required to be static formicrobial growth in aerobic culture, for example, a culture apparatus,such as a culture tank, having a small liquid depth may be used. Whenoxygen demand is large, a submerged culture apparatus may be used, inwhich air is directly passed through an agitation tank or a bubble towerto supply oxygen to the medium.

A method for supplying ammonia to the culture apparatus is not limitedto a particular method; in accordance with the form of ammonia, such asammonia gas, liquid ammonia, or ammonia water, ammonia may be suppliedto the vapor phase of the culture apparatus or supplied into the medium.When ammonia is supplied to the culture apparatus after beingtransformed into the nitrogen-containing compounds originating fromammonia, such as ammonium salts, urea, nitric acid, or nitrates, ammoniamay be supplied into the medium. The supply of ammonia or thenitrogen-containing compound originating from ammonia can be performedin accordance with a known method. The supply amount of ammonia or thenitrogen-containing compound originating from ammonia to the cultureapparatus may be determined in accordance with the specific design ofthe culture apparatus including the type of the microorganism havingorganic compound productivity.

The following describes embodiments of the production system withreference to the accompanying drawings.

FIG. 1 illustrates a production system 1000 including a source gasproduction apparatus 101, an ammonia synthesis apparatus 102, an ammoniaconcentration apparatus 103 selected from a pressurized coolingapparatus and a PSA apparatus, and a culture apparatus 203.

In the production system 1000, first, a hydrogen source gas 1 and air 2are supplied to the source gas production apparatus 101. The hydrogensource gas 1 may be a hydrocarbon (coal, petroleum, natural gas, orbiomass, for example) or water in accordance with a hydrogen productionprocess in the source gas production apparatus 101. Examples of thehydrogen production process can include, as described above, 1) a methodthat transforms a hydrocarbon into gas containing CO and H₂ by a steamreforming reaction, a partial oxidation reaction, or a combination ofthese reactions and then performs a CO shift reaction and decarbonationprocessing, 2) a method that electrolyzes water, and 3) a method thatdecomposes water using a photocatalyst. The source gas productionapparatus 101 also produces nitrogen. Nitrogen may be prepared byseparating nitrogen from air using a nitrogen separation membrane or acryogenic separation method. Alternatively, when hydrogen is preparedutilizing the partial oxidation reaction of the hydrocarbon, nitrogenwithin air used as an oxygen source may be used.

A source gas 3 containing hydrogen and nitrogen produced by the sourcegas production apparatus 101 is supplied to the ammonia synthesisapparatus 102. In the ammonia synthesis apparatus 102, the source gascontaining hydrogen and nitrogen reacts in the presence of the supportedruthenium catalyst to synthesize the ammonia-containing gas.

A synthesized ammonia-containing gas 4 is supplied to the ammoniaconcentration apparatus 103 selected from the pressurized coolingapparatus and the PSA apparatus. When the ammonia concentrationapparatus 103 is the pressurized cooling apparatus, liquid ammonia 6 isobtained. When the ammonia concentration apparatus 103 is the PSAapparatus, concentrated ammonia gas 6 is obtained. The obtained liquidammonia or concentrated ammonia gas may be stored in a storage tank (notillustrated).

The obtained liquid ammonia or concentrated ammonia gas 6 is supplied tothe culture apparatus 203. An appropriate medium in accordance with thetype of the microorganisms having organic compound productivity isintroduced to the culture apparatus 203, and air 13 is supplied theretoas needed. In the culture apparatus 203, the ammonia 6 is used as thenitrogen source or the pH adjuster. The microorganisms having organiccompound productivity is cultured, whereby an organic compound or amicroorganism 14 can be produced.

The production system 1000 illustrated in FIG. 1 includes a recycleapparatus (not illustrated) that recovers unreacted hydrogen andnitrogen separated by the ammonia concentration apparatus 103 andrecycles recovered gas 5 to the upstream side of the ammonia synthesisapparatus 102.

FIG. 2 illustrates a production system 1001 including the source gasproduction apparatus 101, the ammonia synthesis apparatus 102, gasseparation membrane apparatuses (ammonia concentration apparatuses) 104and 105, and the culture apparatus 203. In the production system 1001,the source gas production apparatus 101, the ammonia synthesis apparatus102, and the culture apparatus 203 are as described above.

The production system 1001 includes the gas separation membraneapparatuses 104 and 105 as the ammonia concentration apparatus. Ahydrogen gas separation membrane 104 and a nitrogen gas separationmembrane 105 can be used in combination, for example. The productionsystem 1001 including the gas separation membrane apparatuses 104 and105 can obtain the concentrated ammonia gas 6. The obtained concentratedammonia gas may be stored in a storage tank (not illustrated).

The production system 1001 illustrated in FIG. 2 includes a recycleapparatus that recovers unreacted hydrogen and nitrogen separated by thegas separation membrane apparatuses 104 and 105 and recycles therecovered gas 5 to the upstream side of the ammonia synthesis apparatus102.

FIG. 3 illustrates a production system 1002 including the source gasproduction apparatus 101, the ammonia synthesis apparatus 102, a cooler106, and the culture apparatus 203. In the production system 1002, thesource gas production apparatus 101 and the ammonia synthesis apparatus102 are as described above.

In the production system 1002, the ammonia-containing gas 4 obtained byusing the ammonia synthesis apparatus 102 is cooled by the cooler 106.Next, the cooled ammonia-containing gas 6 is supplied to a premixer 204provided in the culture apparatus 203.

In the production system 1002, the culture apparatus 203 includes thepremixer 204. Between the premixer 204 and the culture tank of theculture apparatus 203, the medium circulates. In the premixer 204,ammonia is premixed with the circulating medium. With this premixing,the medium mixed with ammonia is supplied to the culture tank of theculture apparatus 203.

The cooled ammonia-containing gas 6 contains unreacted hydrogen andnitrogen. The production system 1002 includes a recycle apparatus thatrecovers the unreacted hydrogen and nitrogen in the premixer 204 andrecycles recovered gas 15 to the upstream side of the ammonia synthesisapparatus 102. The recovered gas 15 contains water originating from themedium. In the production system 1002, the recycle apparatus includes adehydrator 107 that removes the water in the recovered gas 15. Theproduction system 1002 also includes a drier 108 that further dries therecovered gas 15.

FIG. 4 illustrates a production system 1003 including the source gasproduction apparatus 101, the ammonia synthesis apparatus 102, thecooler 106, the ammonia water production apparatus 201, an ammoniastripping apparatus 205, and the culture apparatus 203. In theproduction system 1003, the source gas production apparatus 101, theammonia synthesis apparatus 102, the cooler 106, and the cultureapparatus 203 are as described above.

In the production system 1003, the ammonia-containing gas 4 obtained byusing the ammonia synthesis apparatus 102 is cooled by the cooler 106.Next, the cooled ammonia-containing gas 6 is supplied to the ammoniawater production apparatus 201. Water 7 is also supplied to the ammoniawater production apparatus 201. The ammonia water production apparatusdissolves ammonia within the cooled ammonia-containing gas 6 in thewater 7 and can thereby produce ammonia water 8. The method andconditions of dissolution are not limited to particular ones so long asthey can produce ammonia water with an expected concentration; any ofknown methods and conditions may be used.

The cooled ammonia-containing gas 6 contains unreacted hydrogen andnitrogen. The production system 1003 includes a recycle apparatus thatrecovers the unreacted hydrogen and nitrogen in the ammonia waterproduction apparatus 201 and recycles a recovered gas 9 to the upstreamside of the ammonia synthesis apparatus 102. The recovered gas 9contains water originating from the water 7 used in the ammonia waterproduction apparatus 201. In the production system 1003, the recycleapparatus includes a dehydrator 107 that removes the water within therecovered gas 9. The production system 1003 also includes a drier 108that further dries the recovered gas 9.

In the production system 1003, the produced ammonia water 8 is usedfurther for the production of the organic compound or the microorganism.Specifically, the produced ammonia water 8 is supplied to the ammoniastripping apparatus 205 to recover ammonia gas from the ammonia water.The ammonia stripping apparatus 205 is not limited to a particularapparatus so long as it can recover the ammonia gas from the ammoniawater; any of known stripping apparatuses may be used. The ammoniarecovered by the ammonia stripping apparatus 205 is used as the nitrogensource or the pH adjuster, and the microorganism having organic compoundproductivity is cultured in the culture apparatus 203, whereby theorganic compound or the microorganisms 14 can be produced. Water 12removed by the ammonia stripping apparatus 205 may be merged with thewater 7 as illustrated in FIG. 4 or discharged.

The production system 1003 can also transport the ammonia water 8produced by the ammonia water production apparatus 201 and produce theorganic compound or the microorganism at geographically remote sites.

The production systems for an organic compound or a microorganism aredescribed with reference to FIG. 1 to FIG. 4. Although ammonia issupplied to the culture apparatus 203 as the nitrogen source or the pHadjuster in the embodiments illustrated in FIG. 1 to FIG. 4, the ammoniamay be transformed into any of other nitrogen-containing compounds(ammonium salts, urea, nitric acid, or nitrates), and thenitrogen-containing compound may be then supplied to the cultureapparatus 203. Such a modification is also included in the scope of thepresent invention. In the production systems illustrated in FIG. 1 toFIG. 4, a hydrogen supply apparatus such as a hydrogen cylinder or ahydrogen tank and a nitrogen supply apparatus such as a nitrogencylinder or a nitrogen tank may be used in place of the source gasproduction apparatus 101. In the production systems illustrated in FIG.1 to FIG. 3, the concentrated ammonia 6 such as the liquid ammonia orthe concentrated ammonia gas is also suitably supplied to the cultureapparatus 203 after being converted into ammonia water.

Method of Production

The present invention also provides a novel method of production for anorganic compound or a microorganism. The method of production does notinvolve (or minimizes) the transport of liquid ammonia.

In one embodiment, the method of production for an organic compound or amicroorganism can include:

(A) synthesizing an ammonia-containing gas by reaction of a source gascontaining hydrogen and nitrogen in the presence of a supportedruthenium catalyst; and

(B) culturing a microorganism having organic compound productivity usingammonia originating from the obtained ammonia-containing gas.

The supported ruthenium catalyst, the source gas, the ammonia-containinggas used in step (A) and conditions, such as temperature, pressure, andthe like, when the ammonia-containing gas is synthesized are asdescribed in the section here entitled “Production System”. An organiccompound or a microorganism produced in step (B) and the method ofproduction for the same are as described in the section herein entitled“Production System”. The advantageous effects described for theproduction system are also applied to the method of productionsimilarly.

In the method of production, step (A) and step (B) are successivelyperformed. The phrase “step (A) and step (B) are successively performed”can mean that the ammonia-containing gas synthesized in step (A) issubjected to step (B) without being transported as liquid ammonia. Thephrase “being transported as liquid ammonia” can mean transport betweentwo geographically remote sites by pipeline, air, ship, automobile, andthe like and does not include transport within a production site of anorganic compound or a microorganism.

The method of production may further include a process of producing thesource gas containing hydrogen and nitrogen from the hydrogen source gasand air. The methods of production for the hydrogen source gas and thesource gas are as described in the section herein entitled “ProductionSystem.

The method of production may further include a process of concentratingthe ammonia within the ammonia-containing gas obtained in step (A). Themethod for concentrating the ammonia within the ammonia-containing gasis as described in the section herein entitled “Production System.

The method of production may further include a step, hereinafter,referred to as step (C), of recovering unreacted hydrogen and nitrogenand recycling a recovered gas to step (A). In one embodiment, step (C)may include dehydration treatment and/or drying treatment removing waterwithin the recovered gas. The methods of dehydration treatment and thedrying treatment are as described in the section herein entitled“Production System”.

One preferred embodiment of the method of production produces ammoniawater using ammonia originating from the ammonia-containing gas obtainedin step (A) and cultures a microorganism having organic compoundproductivity using the obtained ammonia water in step (B).

Another preferred embodiment of the method of production producesammonia water using ammonia originating from the ammonia-containing gasobtained in step (A), recovers ammonia gas from the obtained ammoniawater, and cultures a microorganism having organic compound productivityusing the recovered ammonia gas in step (B).

The method of production may further include collecting a metabolitefrom a medium liquid after the end of culture. The method for collectingthe metabolite is not limited to a particular method; the metabolite canbe collected by combining an ion exchange resin method, a precipitationmethod, and other methods that have been conventionally commonly known.

EXAMPLES Reference Example 1

<Synthesis of Cs—MgO Supporting Ru>

MgO (manufactured by Ube Material Industries, Ltd., Product No.: UC95)(1 g) was evacuated and heated at 500° C. for 5 hours and was immersedin a tetrahydrofuran solution dissolving Ru₃(CO)₁₂ in an Ar atmosphere.After the mixture was stirred for 3 hours, the solvent was removed by arotary evaporator, and evacuation and heating were performed at 350° C.for 2 hours. With this procedure, a MgO catalyst supporting 2 wt % of Rumetal particles was obtained. Further, the obtained catalyst wasimmersed in an ethanol solution dissolving Cs₂CO₃ in an Ar atmosphere.In this process, the amount of Cs₂CO₃ was adjusted so as to give anelement ratio between Cs and Ru of 1:1. After the mixture was stirredfor 3 hours, the solvent was removed by a rotary evaporator, andevacuation treatment was performed at room temperature for 12 hours toobtain a Cs—MgO catalyst (powder) supporting 2 wt % of Ru metalparticles. The BET specific surface area of the obtained catalyst was 12m²/g. The Ru dispersion (%) measured by a CO adsorption method was 25.

<Ammonia Synthesis Reaction>

A synthesis reaction in which nitrogen gas (N₂) and hydrogen gas (H₂)react to produce ammonia gas (NH₃) was performed. The catalyst obtainedby the above method in an amount of 0.1 g was charged into a glass tube,and the synthesis reaction was performed by a fixed bed flow reactor.The gas flows were set to N₂: 15 mL/min and H₂: 45 mL/min giving a totalof 60 mL/min, and the reaction was performed at a reaction temperatureof 340° C. and a pressure of atmospheric pressure. The gas that hademerged from the flow reactor was bubbled in a 0.005 M aqueous sulfuricacid solution to dissolve the produced ammonia in the solution, and theproduced ammonium ions were quantified by an ion chromatograph.

The 2 wt % Ru/Cs—MgO catalyst (Cs/Ru element ratio=1) showed an ammoniaproduction rate of 2,367 μmolg⁻¹h⁻¹ at 340° C. The TOF(×10⁻³ s⁻¹) was13.3.

Reference Example 2

<Synthesis of Ru—Cs/MgO Catalyst (Catalyst Supporting Cs together withRu on MgO)>

MgO (manufactured by Ube Material Industries, Ltd., Product No.: UC95)powder was put into a quartz glass container and was evacuated at 500°C. for 6 hours to perform dehydration treatment thereon. The dehydratedMgO in an amount of 1.00 g was put into 60 mL of a super dehydrated THFsolvent (manufactured by Wako Pure Chemical Industries, Ltd., ProductNo.: 207-17765). Ru₃(CO)₁₂ (purity: 99%, manufactured by Aldrich,Product No.: 245011) in an amount of 0.02 g was put into the solvent soas to give a Ru support amount of 6 wt % relative to a Ru—Cs/MgOcatalyst, and the mixture was stirred at room temperature for 4 hours tosupport Ru metal on MgO in an impregnated manner. Using an evaporator,the sample was dried and solidified at 40° C. and 16.0 kPa for 7 hours(1.01 g). The dried and solidified sample in an amount of 0.81 g was putinto 100 mL of dehydrated ethanol. Cs₂CO₃ (manufactured by KantoChemical Co., Inc., Product No.: 07184-33) in an amount of 0.078 g wasput thereinto so as to give a molar ratio between Ru and Cs of 1:1, andthe mixture was stirred at room temperature for 4 hours to support Csmetal on Ru/MgO in an impregnated manner. Using an evaporator, thesample was dried and solidified at room temperature and 9.0 kPa for 7hours. A 6 wt % Ru—Cs/MgO catalyst in an amount of 0.087 g was obtained.

<Production of Ammonia Water>

A reaction in which nitrogen gas (Nz) and hydrogen gas (Hz) react toproduce ammonia gas (NH₃) was performed. The obtained catalyst in anamount of 0.2 g was charged into a pressure-resistant tube, and thereaction was performed by a fixed bed flow reactor. The gas flows wereset to N₂: 15 mL/min and H₂: 45 mL/min giving a total of 60 mL/min, andthe reaction was performed at a pressure of 0.9 MPa and a reactiontemperature of 400° C. The gas that had emerged from the flow reactorwas passed through water cooled at about 3° C.; the production rate ofammonia was 3,734 μmolg⁻¹h⁻¹. The produced NH₃ was dissolved in thewater to obtain Aqueous Ammonia 1 (liquid amount: 200 g, NH₄ ⁻ amount:1.60 g) was obtained in about 109 hours.

Reference Example 3

<Production of Ammonium Sulfate Solution>

In the production of ammonia water in Reference Example 2, at a reactiontemperature of 400° C., the reaction pressure was changed from 0.9 MPato 0.1 MPa, and besides, passing the gas that had emerged from thecirculation reactor through the water cooled at about 3° C. was changedto passing the gas that had emerged from the flow reactor through a0.220 M aqueous sulfuric acid solution at room temperature. Ammoniumsulfate was produced similarly to Reference Example 2 except the abovematters. The production rate of ammonia was 3,531 μmolh⁻¹g⁻¹. AmmoniumSulfate Solution 1 (liquid amount: 100 g, NH4⁺ amount: 0.81 g) wasobtained in about 56 hours.

Example 1

The ammonia gas synthesized in Reference Example 1 was dissolved inwater to obtain ammonia water.

Ammonia gas was recovered from the obtained ammonia water using anammonia stripping apparatus, and using the ammonia gas, E. coli MG1655was cultured.

From a growing curve, the ammonia gas obtained was revealed to be ableto be used for fermentation and culture production.

Example 2

Using Aqueous Ammonia 1 produced in Reference Example 2 and E. coli, theproduction culture of L-lysine was performed. The following media wereused for the culture.

LB Agar Medium:

tryptone: 10 g/L, yeast extract: 5 g/L, NaCl: 10 g/L, agar: 15 g/L

Lys Ammoniacal Liquor Medium:

glucose: 20 g/L, NH₃: 3.09 g/L (Aqueous Ammonia 1 produced in ReferenceExample 2 was used), MgSO₄.7H₂O: 1 g/L, KH₂PO₄: 1 g/L, yeast extract: 2g/L, FeSO₄.7H₂O: 0.01 g/L, MnSO₄.5H₂O: 0.008 g/L, adjusted to have a pHof 7.0 using H₂SO₄

Lys-producing bacteria WC196ΔcadAΔldc/pCABD2 were cultured in the LBagar medium with streptomycin added so as to have a final concentrationof 80 mg/L at 37° C. for an entire day and night. All the bacteria onthe plate with a diameter of 90 mm were scraped together from thecultured agar medium and were suspended in 3 mL of a physiologicalsaline solution to prepare a bacteria solution.

The bacteria solution was planted to a thick test tube charged with 5 mLof the Lys ammoniacal liquor medium to which streptomycin had been addedso as to have a final concentration of 80 mg/L and calcium carbonatedry-sterilized in advance had been added so as to have a finalconcentration of 30 g/L so as to have an absorbance at a wavelength of620 nm (O.D. 620 nm) of 0.126, and shake culture was performed at 37° C.and 120 rpm for 24 hours.

Example 3

In Example 2, the Lys ammoniacal liquor medium was changed to thefollowing Lys ammonium sulfate medium. The production culture ofL-lysine was performed similarly to Example 2 except the above matter.

Lys Ammonium Sulfate Medium:

glucose: 20 g/L, (NH₄)₂SO₄: 12 g/L (Ammonium Sulfate Solution 1 producedin Reference Example 3 was used), MgSO₄.7H₂O: 1 g/L, KH₂PO₄: 1 g/L,yeast extract: 2 g/L, FeSO₄.7H₂O: 0.01 g/L, MnSO₄.5H₂O: 0.008 g/L,adjusted to have a pH of 7.0 using KOH

Comparative Example 1

In Example 2, Aqueous Ammonia 1 in the Lys ammoniacal liquor medium waschanged to commercially available aqueous ammonia (manufactured byJunsei Chemical Co., Ltd., Product No.: 13370-0301). The productionculture of L-lysine was performed similarly to Example 2 except theabove matter.

Comparative Example 2

In Example 3, Ammonium Sulfate Solution 1 in the Lys ammonium sulfatemedium was changed to a commercially available ammonia sulfate solution(manufactured by Junsei Chemical Co., Ltd., Product No.: 83110-0367).The production culture of L-lysine was performed similarly to Example 3except the above matter.

TABLE 1 Production O.D. amount of Nitrogen 620 nm L-lysine Yeild source(xl) (g/L) (%) Example 2 Aqueous 8.31 ± 0.05 8.3 ± 0.0 39.6 ± 0.2Ammonia 1 Example 3 Ammonium 9.95 ± 0.10 8.4 ± 0.0 39.5 ± 0.2 SulfateSolution 1 Comparative Aqueous 8.45 ± 0.13 8.4 ± 0.1 39.5 ± 0.3 Example1 Ammonia (commercially available product) Comparative Ammonium 10.22 ±0.06  8.7 ± 0.1 40.2 ± 0.3 Example 2 Sulfate Solution (commerciallyavailable product)

The culture results are listed in the above table. Also when AqueousAmmonia 1 produced in Reference Example 2 or Ammonium Sulfate Solution 1produced in Reference Example 3 was used, bacterial growth and theproduction of L-lysine substantially equal to those of the examplescultured using the commercially available aqueous ammonia (ComparativeExample 1) or the commercially available ammonium sulfate solution(Comparative Example 2) were revealed, showing that the ammonia gas canbe used for fermentation and culture production.

Example 4

Using Aqueous Ammonia produced in Reference Example 2 andCorynebacterium glutamicum, the production culture of L-glutamic acidwas performed. The following media were used for the culture.

CM-Ace Agar Medium:

glucose: 2.5 g/L, fructose: 2.5 g/L, sodium gluconate: 4 g/L, sodiumsuccinate.6H₂O: 2 g/L, peptone: 10 g/L, yeast extract: 10 g/L, KH₂PO₄: 1g/L, MgSO₄.7H₂O: 0.4 g/L, FeSO₄.7H₂O: 0.01 g/L, MnSO₄.5H₂O: 0.01 g/L,urea: 4 g/L, bean filtrate (soybean hydrolysate): 1.2 g/L (T-N), biotin:1 mg/L, vitamin B1: 5 mg/L, adjusted to have a pH of 7.5 using KOH

Glu Ammoniacal Liquor Medium:

glucose: 40 g/L, NH₃ (Aqueous Ammonia 1 produced in Reference Example 2was used): 3.86 g/L, KH₂PO₄: 1 g/L, MgSO₄.7H₂O: 0.4 g/L, FeSO₄.7H₂O:0.01 g/L, MnSO₄.5H₂O: 0.01 g/L, vitamin B1: 200 μg/L, biotin: 300 μg/L,bean filtrate: 0.48 g/L (T-N), K₂SO₄: 19.78 g/L, adjusted to have a pHof 8.0 using H₂SO₄

Glu producing bacteria 2256ΔldhAΔsucAyggB* of Corynebacterium glutamicumwere cultured in the CM-Ace agar medium at 31.5° C. for an entire dayand night. The bacteria corresponding to 1/24 plate were scraped fromthe agar medium after culture and were planted to a thick test tubecharged with 5 mL of the Glu ammoniacal liquor medium to which calciumcarbonate dry-sterilized in advance had been added so as to have a finalconcentration of 30 g/L, and shake culture was performed at 31.5° C. and120 rpm for 24 hours.

Example 5

In Example 4, the Glu ammoniacal liquor medium was changed to thefollowing Glu ammonia sulfate medium. The production culture ofL-glutamic acid was performed similarly to Example 4 except the abovematter.

Glu Ammonium Sulfate Medium:

glucose: 40 g/L, (NH₄)₂SO₄: 15 g/L (Ammonium Sulfate Solution 1 producedin Reference Example 3 was used), KH₂PO₄: 1 g/L, MgSO₄.7H₂O: 0.4 g/L,FeSO₄.7H₂O: 0.01 g/L, MnSO₄.5H₂O: 0.01 g/L, vitamin B1: 200 μg/L,biotin: 300 μg/L, bean filtrate: 0.48 g/L (T-N), adjusted to have a pHof 8.0 using KOH.

Comparative Example 3

In Example 4, Aqueous Ammonia 1 in the Glu ammoniacal liquor medium waschanged to commercially available aqueous ammonia (manufactured byJunsei Chemical Co., Ltd., Product No.: 13370-0301) The productionculture of L-glutamic acid was performed similarly to Example 4 exceptthe above matter.

Comparative Example 4

In Example 5, Ammonium Sulfate Solution 1 in the Glu ammonium sulfatemedium was changed to a commercially available ammonium sulfate solution(manufactured by Junsei Chemical Co., Ltd., Product No.: 83110-0367).The production culture of L-glutamic acid was performed similarly toExample 5 except the above matter.

TABLE 2 Production O.D. amount of Nitrogen 620 nm L-glutamic Yieldsource (xl) acid (g/L) (%) Example 4 Aqueous 31.93 ± 0.54 20.4 ± 0.051.8 ± 0.0 Ammonia 1 Example 5 Ammonium 27.57 ± 0.48 20.8 ± 0.1 50.2 ±0.1 Sulfate Solution 1 Comparative Aqueous 33.59 ± 0.56 20.8 ± 0.2 48.6± 0.5 Example 3 Ammonia (commercially available product) ComparativeAmmonium 29.65 ± 0.68 21.8 ± 0.0 51.2 ± 0.0 Example 4 Sulfate Solution(commercially available product)

The culture results are listed in the above table. Also when AqueousAmmonia 1 produced in Reference Example 2 or Ammonium Sulfate Solution 1produced in Reference Example 3 was used, bacterial growth and theproduction of L-glutamic acid substantially equal to those of theexamples cultured using the commercially available aqueous ammonia(Comparative Example 3) or the commercially available ammonium sulfatesolution (Comparative Example 4) were revealed, showing that the ammoniagas obtained can be used for fermentation and culture production.

REFERENCE SIGNS LIST

1 Hydrogen source gas

2 Air

3 Source gas containing hydrogen and nitrogen

4 Ammonia-containing gas

5, 9, 15 Recovered gas

6 Concentrated ammonia

7 Water

8 Ammonia water

12 Water removed by ammonia stripping apparatus

13 Air

14 Organic compound or microorganism

101 Hydrogen/nitrogen production apparatus

102 Ammonia synthesis apparatus

103 Ammonia concentration apparatus

104, 105 Gas separation membrane

106 Cooler

107 Dehydrator

108 Drier

201 Ammonia water production apparatus

203 Culture apparatus

204 Premixer

205 Ammonia stripping apparatus

1000, 1001, 1002, 1003 Production system for organic compound ormicroorganism

1. A production system useful for reacting a source gas and a rutheniumcatalyst to produce an organic compound or a microorganism, theproduction system comprising: A) an ammonia synthesis apparatusconfigured to react a source gas comprising hydrogen and nitrogen in thepresence of a ruthenium catalyst and a support, wherein anammonia-containing gas is synthesized; and B) a culture apparatusconfigured to culture a microorganism able to produce an organiccompound using ammonia originating from said ammonia-containing gas. 2.The production system according to claim 1, wherein said ammoniasynthesis apparatus is configured to react the source gas underconditions comprising a reaction temperature of 530° C. or lower and areaction pressure of 30 MPa or lower.
 3. The production system accordingto claim 1, further comprising an ammonia concentration apparatus thatis configured to concentrate the ammonia from the ammonia-containinggas.
 4. The production system according to claim 1, further comprising arecycle apparatus that is configured to recover unreacted hydrogen andnitrogen following said reaction in the ammonia synthesis apparatus, andis also configured to return said unreacted hydrogen and nitrogen to bereacted again in the ammonia synthesis apparatus.
 5. The productionsystem according to claim 4, wherein the recycle apparatus comprises adehydrator and/or a drier configured to remove water from said unreactedhydrogen and nitrogen.
 6. The production system according to claim 1,wherein the production system is configured to produce ammonia waterusing the ammonia originating from said ammonia-containing gas and isalso configured to culture a microorganism able to produce an organiccompound using said ammonia water.
 7. The production system according toclaim 1, wherein the production system is configured to: produce ammoniawater using the ammonia originating from said ammonia-containing gas,recover ammonia gas from said obtained ammonia water, and culture amicroorganism able to produce an organic compound using said ammoniagas.
 8. The production system according to claim 1, wherein ammonia isused as a nitrogen source or a pH adjuster in the culture apparatus. 9.The production system according to claim 1, wherein the microorganism isable to produce an organic compound selected from the group consistingof amino acids, organic acids, polysaccharides, proteins, antibiotics,and alcohols.
 10. The production system according to claim 1, whereinthe microorganism is a bacterium or a fungus.
 11. A method of productionfor a product selected from the group consisting of an organic compoundand a microorganism, the method comprising the steps of: (A) reacting asource gas comprising hydrogen and nitrogen in the presence of aruthenium catalyst and a support, wherein an ammonia gas is synthesized;and (B) culturing a microorganism able to produce an organic compoundusing ammonia originating from said ammonia-containing gas.
 12. Themethod according to claim 11, wherein step (A) and step (B) aresuccessively performed.
 13. The method according to claim 11, whereinthe source gas reacts under conditions comprising a reaction temperatureof 530° C. or lower and a reaction pressure of 30 MPa or lower in step(A).
 14. The method according to claim 11, further comprisingconcentrating ammonia within the ammonia-containing gas obtained in step(A).
 15. The method according to claim 11, further comprising recoveringunreacted hydrogen and nitrogen after step (A) and recycling saidunreacted hydrogen and nitrogen to step (A).
 16. The method according toclaim 15, wherein the recycling comprises performing dehydrationtreatment and/or drying treatment to remove water from said unreactedhydrogen and nitrogen.
 17. The method according to claims 11, whereinammonia water is produced using ammonia originating from theammonia-containing gas obtained in step (A) and a microorganism able toproduce an organic compound is cultured using the obtained ammonia waterin step (B).
 18. The method according to claims 11, wherein ammoniawater is produced using ammonia originating from the ammonia-containinggas obtained in step (A), ammonia gas is recovered from the obtainedammonia water, and a microorganism able to produce organic compound iscultured using said ammonia gas in step (B).
 19. The method according toclaims 11, wherein ammonia is used as a nitrogen source or a pH adjusterin step (B).
 20. The method according to claims 11, wherein themicroorganism is able to produce an organic compound selected from thegroup consisting of amino acids, organic acids, polysaccharides,proteins, antibiotics, and alcohols.
 21. The method according to claim11, wherein the microorganism is a bacterium or a fungus.